Color photographic silver halide emulsion



.6 Claims. c1. 96-100) ABSTRACTO F THE DISCLOSUE A color photographic silver halide emulsion as a coupler a compound of the formula:

containing CHflCHDn CO II NCHzCHsC O-A CHI(CHZ)I wherein the A represents a coupling component having at least one groupselected from the class consisting of ;ketomethylene The present invention relates to color-photographic materials, and more particularly it relates to photographic materials containing, so-called, protected couplers' Filed Feb. 17, 1964, Ser. No. 345,120

I group, pyrazolon nucleus and phenolic hydroxyl group; the n represents an integer of from 6 to 12.

v( United StatesPatent 0 F As is well known, in color photographic processes of i the incorporated type, a water soluble coupler is dissolved in water'and dispersed in the photographic emulsion in the form of an aqueous solution, or an oil soluble'coupler is dissolvedin an oil and. dispersed into the photographic emulsion in the form of solution in organic solvents. In the latter method, the following matters are important factors, i.e., the coupler employedhas high solubility in organic solvents for dispersion and it has high dispersibility during and after coatingit as photosensitive material on a supporting material. j

An object of the present invention'is' to provide a processemployingas'a coupler a compound which has'high solubility in solvents with a high boiling point which are difiicultly soluble in water, and which does not cause unequalness of coating or lowering of the quality of the image by deposit of the precipitate or aggregation during and after the usual process for the production of photosensitive materials, or after developing treatment, such as butyl phthalate, o-tolyl pht'halate, butyl phosphate and the like;

We have found that the following compounds represented by the general formula are suitably used for this purpose. I I

I CH3(CHI)nCO N CHQCHC O-A case i)! wherein the A represents a coupling component having at least one keto-methylene group and phenolic hydroxyl group such as pyrazolone, phenol, and naphthol nuclei;

I the n represents an integer of 6-12. In the case where n Compounds which may be usedacording to, the present invention are explained as follows:

I 3,337,344 Patented Aug. 22, 1967 couucmoumncoomcrnn custom m cH| cH,)Bco p KNCIhCmCONHOCOCH CO NHQ H i C :(C a): I I 7 CH: I v I (2) v K HzhoCQ I NcrnorncoNHOooomooNn I canon- 8 I cm "ornwrmtoo I I NCH:CHxCONH1(|3-CH| cane c=o K QuCO I I NCHzCHzCONI-I?-GH| CHI-MC 2): =0

In order to prove that the compounds havin'g'the above general formula, respectively have excellent solubility, the melting point and the solubility; measured by dissolving the compounds in g. of butyl phthalate at 25 C., of the said: compounds 1, 2 and 5, respectively, are compared with those of compounds having a similar structure and containing a straight alkyl chain. The compounds to be employed for the comparison have the following structure.

C QNHOHnCHzNHC O (CHzhaCHz cuxcmmoounOoocmcomrQ I 0, H:

Examples'of synthesis of the compounds of the present invention and examples of the process for the production of photosensitive materials therefrom are shown in the following:

' (1) Synthesis ofthe compounds 7 I v 174 g. of methyl acrylate is mixed with 146 g. of butylamine at room temperature and allowed to stand. The reaction proceeds exothermically. -After the reaction in avessel provided with arefluxing condenser, the product is heated at 70 C.- on a steam bath. Then, the reaction is completed. The'reaction product is distilled under a reduced pressure, to yield methyl 3-(butyl amino) propionate with an almost quantitative yield. The boiling pointof the product is 75 C./5 mm. Hg and the yield is 300 g.

159 g. of thus prepared methyl 3-(butyl amino) propionate and 120 g. of triethylamine are dissolved in 1.5 liter of ether and dropped with 246 g. of myristic chloride under stirring while cooling with ice. It takes about 2 hours for dropping. After dropping, the mixture is stirred at room temperature for 30 minutes and the formed triethylaminine hydrochloride is filtered oil. The ether solu'-' 'tion is washed well with water, dried and distilled under vacuum. A distillate having a boiling point of 196-8 3 ./1 mm. Hg is separated. 305 g. of methyl 3-(N-butyl tetradecanamido)-propionate is obtained. The yield is 82.5%..

305 g. of the thus prepared ester is added into an alcoholic solution of 60 g. of potassium hydroxide and heated" for 1 hour to reflux. Thereafter, alcohol is distilledoff and the residual. solution is added to 120ml. of concentrated hydrochloric acid and 100 ml. of'water; The

,formedacid is separated and extracted'by 1 liter of ether.

After drying the extract with anhydrous sodium sulfate, the solvent is distilled off, to yield 285 g. of 3-(N-butyl tetradecanamido)-propionic acid. 35.5 g. of the resulting 3-(N-butyltetradecanamido)-propionic acid is added with 11.8 g. of thionyl chloride and heated on a steam bath, to react violently. Then, thecorresponding acid chloride is obtained. The whole amount of acid chloride, 23 g. of N-(Z-aminoethyl)-1-hydroxy-2-naphthamide and g. of

pyridine are mixed and reacted at a high temperature.

With progress of the reaction, the suspended raw materials transfer to the solution. After the completion of addition, the formed triethylamine hydrochloride is filtered off. Part of the acetoneis distilled off from the filtrate. The residual solution is poured into ice water. The

separated'oily product is washed with water and added with a small amount of methanol, to effect crystallization. Recrystallization is carried out by use of aqueous methanol and'then methanol. 16 g. of crystals having a melting point of 90 C. is obtained.

(3) Synthesis of the compound 3 is produced as a distillate having a boiling point of 171Z- -3 C./0.5 mm. Hg from 15 g. of methyl 3-(butylamino) propionate, 120 g. of triethylamine and 218.5 g. of lauric chloride by the same treatment asi-rr'Example 1. The thus prepared methyl=3-(N-butyldodecanamido)propionate is hydrolyzed to yield 248 g. of the corresponding carboxylic acid. 19 g. of the compound 3 with a melting point of 110 C. is-produced by reacting the corresponding acid with. 3-aminobenzoylaceto-Z-methoxyanilide in the same manner asin Example 2.

(4) Synthesis of the compound 4 1, Methyl B-(N-butyloctanamido)propionate is produced from 123 g. of methyl 3-(butylamino)propionate, 120 g. of triethylamine and 118 g. of caprylic chloride by the same process as in-Example l. The ether solution of this ester is not distilled under vacuum after distillation of the solvent. The solution is subjected to hydrolysis with a solution containing 50 g.- of potassium hydroxide. After neutralization, the separated carboxylic acid is distilled in vacuo. 55 g. of the distillate having a boiling point of 190-205 C.'/,3 mm. Hg is obtained.

27 g. of the carboxylic acid is added with 12 g. of thionyl chloride and reacted on a steam bath, to'yield crude acid chloride. The crudc a'cid chloride is subjected After allowing the reaction product to stand overnight,

the reaction productis poured into dilute hydrochloric acid. The separated oily material is washed with water and then added to 10 ml. of .nitroethane. After cooling and allowing the mixture to stand for about hours, crystals in the form of a lump are separated. By recrystallizing the crystals twice with methanol, 5 g. of the pure product having a melting point of 67 C. is obtained.

(2)- Synthesis of the compound 2 When the product is hydrolyzed by the same treatruent as mentioned above, 210 g. of the corresponding acid is obtained. By reacting 30 g. of the thus prepared acid with 11.8 g. of thionyl chloride, the acid chloride is obtained. 28 g. of 4-aminobenzoylaceto-2-methoxyanilide is suspended in 200 ml. of acetone and added with 15 g. of triethylamine. Under stirring, the mixture is added to an acid chloride solution in acetone at room temperature.

td'the following treatments without purification processes. The above acid chloride is added to 17 g.'of 1-phenyl-3- 'a rnino-S-pyrazoIone and 20 ml.-'of diethyl oxalate, and heated on a steam bath. After a while, solid materials become dissolved or molten. After preparing a homogeneous mass, it is poured into water. Then, the separated oily product is washed with Water and mixed with a small amount of methanol to crystallize. Recrystallization is carried out by use of methanol and then ethanol. 183 g. of crystals having a melting point of 183 C. is obtained.

(5 Synthesis of the compound 5 Acid chloride is prepared by reacting 35.5 g. of 3-(N- butyltetradecanamido)-propionic acid produced in Example 1 with 11.8 g. of thionyl chloride. The acid chloride is mixed with 28 g. of 1-(2,4,6-trichlorophenyl-3-amino- S-pyrazolone) and 20 ml. of diethyl oxalate and mixed well on a steam bath at an elevated temperature. With the progress of the reaction, the mixture becomes molten. After making a homogeneous mass, the reaction mixture is poured into water. Water is decanted off from the separated oily product. The process is repeated twice. The resulting product is crystallized by means of addition of a small amount of methanol. By recrystallization of the crystals with acetonitrile twice, 7 g. of the product having the melting point of 106 C. is obtained.

EXAMPLE 1 8 g. of the compound 1 is dissolved in 20 g. of butylphthalate. The solution is added to 10 ml. of a 5% saponin aqueous solution and 200 ml. of a 5% gelatine aqueous solution. After emulsification, the solution is added to 500 g. of iodobromide emulsion, coated on a film base and dried. After exposing this color photographic materials, it is developed with a developer consisting of the following components.

G. 2-amin0-5-N,N-diethylaminotoluene hydrochloride 2.0 Sodium sulfite 2.0 Sodium carbonate 20.0 Potassium bromide 2.0

Water, to make 1 liter.

The developed film is bleached and fixed. A cyan image having the maximum absorption at 700 Nm. is obtained. Aggregation of coupler or dye is not observed during the whole processes or in the formed image.

EXAMPLE 2 10 g. of the compound 2 is dissolved in 20 g. of butylphthalate and treated in the same way as in Example 1. A yellow image having the maximum absorption at 442 Nm. is produced. In the whole processes and in the formed color image, aggregation of coupler or dye is not found.

EXAMPLE 3 10 g. of the compound 5 is dissolved in 20 g. of butylphthalate. The solution is added into 150 ml. of a 2% gelatin aqueous solution, and passed through a colloid mill to disperse. The resulting solution is added to 1000 g. of a positive emulsion, coated on a film base and dried. The thus prepared color photographic material is exposed to light and developed with a developer consisting of the following components.

G. N,N-diethyl-p-phenylenediamine 2.0 Sodium sulfite 2.0 Sodium carbonate 20.0 Potassium bromide 1.0

Water, to make 1 liter.

The developed film is bleached and fixed. A magenta image having the maximum absorption at 553 Nm. is obtained. In the whole processes and in the formed color image, aggregation of coupler and dye is not observed.

EXAMPLE 4 7 g. of the compound 4 is dissolved in 20 g. of butylphosphate and treated by the same process as in Example 1. A magenta image having the maximum absorption at 545 Nm. is obtained. Aggregation of coupler and dye is not observed in the whole processes or in the produced color image.

What we claim is:

1. A color photographic silver halide emulsion, which is characterized in that a compound represented'by the following general formula is contained as a coupler,

OH3(CH2)nCO N CH2CH2C -13.

CHM-3H2):

wherein the A represents a coupling component having at least one group selected from the class consisting of ketomethylene group, pyrazolon nucleus and phenolic hydroxyl group; the n represents an integer of from 6 to 12.

2. A color photographic silver halide emulsion according to claim 1, wherein the compound is represented by the general formula of I O(C 2)uCH:

C ONH CHQOHZNHC O CHzCHgN 3. A col-or photographic silver halide emulsion according to claim 1, wherein the compound is represented by the general formula of CHa(CHg)aG O OCH;

4. A color photographic silver halide emulsion according to claim 1, wherein the compound is represented by the general formula of ;NCHaCHzCONH-O-GOCHaCONH CH C 5. A color photographic silver halide emulsion according to claim 1, wherein the compound is represented by the general formula of CH (CH) N 0:0

6. A color photographic silver halide emulsion according to claim 1, wherein the compound is represented by the general formula of J. TRAVIS BROWN, Primary Examiner.

ENCHzCH CONH-OC ocrno ONE-O 

1. A COLOR PHOTOGRAPHIC SILVER HALIDE EMULSION, WHICH IS CHARACTERIZED IN THAT A COMPOUND REPRESENTED BY THE FOLLOWING GENERAL FORMULA IS CONTAINED AS A COUPLER, 